EP1615853B1 - Procede de fabrication d'hydroxosulfates de cuivre et compositions fongicides cupriques les contenant - Google Patents

Procede de fabrication d'hydroxosulfates de cuivre et compositions fongicides cupriques les contenant Download PDF

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Publication number
EP1615853B1
EP1615853B1 EP04742496.5A EP04742496A EP1615853B1 EP 1615853 B1 EP1615853 B1 EP 1615853B1 EP 04742496 A EP04742496 A EP 04742496A EP 1615853 B1 EP1615853 B1 EP 1615853B1
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EP
European Patent Office
Prior art keywords
copper
weight
aqueous
brochantite
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP04742496.5A
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German (de)
English (en)
French (fr)
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EP1615853A2 (fr
Inventor
Frédéric Ferrier
Gérard Joncheray
Marc Pillot
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cerexagri SA
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Cerexagri SA
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Publication date
Application filed by Cerexagri SA filed Critical Cerexagri SA
Publication of EP1615853A2 publication Critical patent/EP1615853A2/fr
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Publication of EP1615853B1 publication Critical patent/EP1615853B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/10—Sulfates

Definitions

  • the present invention relates to the field of phytosanitary products and more particularly to a process for producing aqueous suspensions of copper hydroxosulfates such as brochantite and antlerite, or a mixture of both, with a high copper content by weight, and their use for the preparation of cupric fungicidal compositions in the form of powders, granules or concentrated suspensions, dispersible in water.
  • copper hydroxosulfates such as brochantite and antlerite, or a mixture of both
  • Copper hydroxosulphates represent the active ingredient of the Bordeaux mixture.
  • Bordeaux mixture is one of the oldest fungicides used to control downy mildew. Its use results from the observation of Alexis Millardet, professor at the Faculty of Bordeaux, who highlighted in 1885 the effectiveness of this preparation cupric on the mildew of the vine (plasmopara viticola).
  • Bordeaux mixture is an essential part of fungicidal copper preparations. Its protection against vine downy mildew and its complementary actions such as the limitation of gray mold, powdery mildew, acid rot and bacterial tumors make this cupric preparation a major product of the protection of the vine. In arboriculture, the Bordeaux mixture has efficiencies on apple and pear against European canker, scab and fire blight. On peach and nectarine, it is used against blisters, bacterial dieback. The diversity of its uses is also true in the case of market gardening. For example, it can be used against mildew and tomato bacterias or against angular leaf spot diseases and purple and red spots on strawberries. Its effectiveness against the downy mildew of the vine, its multiple complementary actions on other phytopathogenic organisms and its low phytotoxicity make the Bordeaux mixture one of the most versatile fungicides of the phytosanitary protection.
  • the fungicidal efficacy of the Bordeaux mixture and its lack of phytotoxicity is related to its polyphase composition of copper complexes (also called copper hydroxosulphates), among which brocantite of formula Cu 4 (SO 4 ) (OH) 6 and antlerite of formula Cu 3 (SO 4 ) (OH) 4 .
  • copper complexes also called copper hydroxosulphates
  • These copper hydroxosulfates release, according to a slow and constant kinetics of cupric ions in the environment of the parasite, which confers on the Bordeaux mixture a fungicidal activity unequaled by the other fungicidal copper forms, such as copper hydroxide or copper oxychloride. , and an optimal compromise efficiency - no phytotoxicity.
  • a classic Bordeaux mixture consists, in addition to a mixture of copper hydroxosulfates, of a polyphase mixture of calcium complexes, by-products inherent to its synthesis made from copper sulphate and lime.
  • the weight content of active ingredient represented by the cupric ion does not exceed 27.3%.
  • the copper content of the Bordeaux mixture compositions can not exceed 25% by weight and generally has a value of 20% by weight, unlike other copper-copper or copper oxychloride-based copper formulations, of which the copper content can reach 40% or even 50% by weight. This is due to the fact that the cupric copper hydroxide or copper oxychloride forms respectively possess 65% and 58% by weight of cupric ion.
  • Brochantite and antlerite can also be obtained from the reaction of cupric oxide with copper sulfate according to the following equations: 3 CuO + CuSO 4 + 3H 2 O ⁇ Cu 4 (OH) 6 SO 4 2 CuO + CuSO 4 + 2H 2 O ⁇ CU 3 (OH) 4 SO 4
  • the invention therefore firstly relates to a process for producing aqueous suspensions of brochantite (Cu 4 (OH) 6 SO 4 ) or antlerite (Cu 3 (OH) 4 SO 4 ) or a mixture of both , having a solids content of greater than 10%, by reaction of an aqueous CuSO 4 copper sulphate solution with an aqueous suspension of copper oxide or copper hydroxide used in a SO 4 / Cu molar ratio total ranging from 0.25 to 0.40, said process being characterized in that an aqueous solution of CuSO 4 having a weight concentration of copper of between 6% and 10% is mixed with an aqueous suspension of copper oxide or copper hydroxide having a concentration of between 15% and 50% by weight and the average diameter of the solid particles is less than 25 microns, the reaction being carried out at a controlled temperature between 40 ° C and 100 ° C.
  • Aqueous suspensions of copper hydroxosulfates such as brochantite or antlerite or a mixture of both are obtained according to the process of the invention from an aqueous solution of copper sulphate and an aqueous suspension of copper oxide or copper hydroxide used with a SO 4 / Cu molar ratio, where Cu represents the number of moles of copper in all forms, between 0.25 and 0.40.
  • the weight content of copper of the aqueous solution of copper sulphate introduced into the reaction medium may vary between 6% and 10%. However, it is preferable to use an aqueous solution of copper sulphate with a copper content of between 6.5% and 8% and, more particularly, between 6.6% and 7.6%.
  • the aqueous suspension of copper oxide or copper hydroxide used in the process has a concentration of between 15% and 50% by weight, preferably between 20% and 30% by weight.
  • the diameter of the particles of the aqueous suspension of copper oxide or copper hydroxide is a critical parameter which conditions the good reaction flow. A grinding is generally carried out under conditions known to those skilled in the art to significantly increase the specific surface area of these suspensions and thus their reactivity.
  • the aqueous suspension of copper oxide or copper hydroxide a particle size of which the average diameter of the solid particles is less than 25 ⁇ m, preferably between 0.1 and 10 ⁇ m and more particularly between 0 , 5 and 5 microns and whose refusal to wet sieving to 25 microns relative to the solids content is less than 5% by weight, and more particularly less than 2% by weight (according to the CIPAC method MT 59.3).
  • Grinding of the copper oxide or copper hydroxide in suspension can be carried out optionally in the presence of copper sulfate.
  • the presence of copper sulphate in the aqueous suspension of copper oxide or copper hydroxide makes it possible to optimize the grinding of the copper oxide in acidic medium, and consequently to increase its reactivity.
  • the aqueous solution of copper sulphate and the aqueous suspension of copper oxide or copper hydroxide described above are mixed in the process according to the invention after having been one and / or the other previously brought (s) at an initial temperature of not more than 100 ° C.
  • the order of addition of the reagents is not a critical parameter for obtaining brochantite, but for the sole production of antlerite it is necessary that the aqueous suspension of copper oxide or hydroxide copper is added to the aqueous solution of copper sulphate previously brought to an initial temperature at most equal to 100 ° C.
  • a sulfuric acid solution can be used instead of the aqueous solution of copper sulphate.
  • the solubilization of copper oxide or copper hydroxide in the acid medium leads in situ to the formation of copper sulfate.
  • the residual sulfuric acid concentration may be between 0 and 1% by weight.
  • the initial temperature of the reaction medium is less than or equal to 60.degree. preferably between 40 ° C and 60 ° C; the initial temperature of the reaction medium is maintained for a period of between one hour and 3 hours, then the reaction medium is brought to a higher temperature maintained for at least one hour.
  • the upper temperature at which the reaction medium is heated is at most equal to 100 ° C., preferably between 65 ° C. and 80 ° C.
  • This variant is preferred because it is suitable for the manufacture of aqueous brocantite suspensions having a solids content greater than 10% by weight.
  • the reaction can lead to an increase in viscosity which can limit the homogenization of the suspension.
  • a dilution by adding water can be carried out so as to reduce the level of dry matter in the mixture.
  • an aqueous solution of copper sulphate and an aqueous suspension of copper oxide or hydroxide with a total SO 4 / Cu molar ratio ranging from 0.25 to 0.34 are used.
  • the initial temperature of the reaction medium is between 70 ° C. and 100 ° C., preferably between 80 ° C. and 90 ° C. This temperature is maintained for a period of between 0.5 hours and 3 hours.
  • the aqueous suspension of copper oxide or copper hydroxide it is necessary for the aqueous suspension of copper oxide or copper hydroxide to be added to the aqueous solution of copper sulphate previously brought to the initial temperature.
  • the excess copper sulfate is filtered off or neutralized.
  • the neutralization of excess copper sulphate can be done by any organic or mineral base.
  • organic bases that may be mentioned are the salts of carboxylic or polycarboxylic acids in which the cation may be sodium, potassium or ammonium.
  • organic bases include amines.
  • mineral bases that may be mentioned are soda, potassium hydroxide, lime, ammonia, sodium carbonate or potassium carbonate.
  • the reaction product is in the form of an aqueous suspension whose solids content by weight is greater than 10% and whose weight content of copper of the solid phase, consisting of at least 85% of copper hydroxosulfates, is greater than 48%.
  • the weight content of the suspension can be increased by a concentration step (centrifugation or decantation).
  • the dough thus obtained can be used for the manufacture of fungicidal formulations of SC type (concentrated liquid suspension), SE (suspo-emulsion) or WG type (granules), dispersible in water and stable storage.
  • the paste obtained after concentration needs to be dried.
  • the drying of the dough can be carried out using any type of dryer known to those skilled in the art in order to obtain a powder with less than 1% moisture content.
  • An interesting alternative is the fluidification of the dough by any chemical agent known to those skilled in the art.
  • the fluidized paste can then be spray-dried.
  • the invention also relates to a process for the preparation of commercially required copper fungicidal compositions using aqueous suspensions of brochantite or antlerite or a mixture of both prepared according to the method described above, in the form of fluidized paste or powder, used as fungicides alone or in combination with other fungicidal organic synthetic materials.
  • cupric fungicidal compositions The manufacture of the cupric fungicidal compositions is carried out in a manner known per se using the usual adjuvants (dispersants, wetting agents, defoamers, dyes, thickeners, inert fillers, pH corrector).
  • the fungicidal organic synthetic materials are chosen from, in particular, compounds whose F-ISO common names are mancozeb, maneb, zineb, cymoxanil, famoxadone and benthiavalicarb.
  • copper-containing fungicidal formulations with a copper content of between 30 and 45%, or between 15% and 40%, preferably between 18% and 40%, are obtained. and 40%, depending on whether copper hydroxosulfates are fungicidal alone or in combination with other active ingredients.
  • the effectiveness of the treatment is determined by evaluating, on the one hand, the percentage of vine leaves affected by late blight and the percentage of leaf area destroyed, on the other hand, the percentage of clusters affected and the percentage of destroyed crop.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Pest Control & Pesticides (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
EP04742496.5A 2003-04-16 2004-04-14 Procede de fabrication d'hydroxosulfates de cuivre et compositions fongicides cupriques les contenant Expired - Lifetime EP1615853B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0304784A FR2853894B1 (fr) 2003-04-16 2003-04-16 Procede de fabrication d'hydroxosulfates de cuivre et compositions fongicides cupriques les contenant
PCT/FR2004/000913 WO2004094315A2 (fr) 2003-04-16 2004-04-14 Procede de fabrication d’hydroxosulfates de cuivre et compositions fongicides cupriques les contenant

Publications (2)

Publication Number Publication Date
EP1615853A2 EP1615853A2 (fr) 2006-01-18
EP1615853B1 true EP1615853B1 (fr) 2018-10-03

Family

ID=33041921

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04742496.5A Expired - Lifetime EP1615853B1 (fr) 2003-04-16 2004-04-14 Procede de fabrication d'hydroxosulfates de cuivre et compositions fongicides cupriques les contenant

Country Status (12)

Country Link
US (1) US8911794B2 (uk)
EP (1) EP1615853B1 (uk)
CN (1) CN100556814C (uk)
AU (1) AU2004232514B2 (uk)
BR (1) BRPI0409445B1 (uk)
FR (1) FR2853894B1 (uk)
MX (1) MXPA05011119A (uk)
NZ (1) NZ543412A (uk)
RU (1) RU2362740C2 (uk)
UA (1) UA80480C2 (uk)
WO (1) WO2004094315A2 (uk)
ZA (1) ZA200508935B (uk)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2917983B1 (fr) * 2007-06-27 2011-05-13 Olmix Nouveaux materiaux composites, leur procede de preparation et leurs utilisations.
MD3583C2 (ro) * 2008-02-12 2008-12-31 Георге ДУКА Procedeu de obţinere a compoziţiei fungicide ultradisperse
CN102815740B (zh) * 2012-08-03 2015-04-22 西北矿冶研究院 提高硫酸铜品级的生产方法
CL2013000332A1 (es) * 2013-02-01 2013-03-08 Compañia Minera San Geronimo Matriz impregnable de origen vegetal, animal o sintetica que contiene un compuesto antimicrobiano distribuido homogeneamente; procedimiento para impregnar un compuesto en una matriz; uso de dicha matriz para preparar soportes solidos de uso cosmetico, farmaceutico, medico o veterinario.
CN105991285B (zh) * 2015-02-16 2019-06-11 阿里巴巴集团控股有限公司 用于量子密钥分发过程的身份认证方法、装置及系统
IT201600092692A1 (it) * 2016-09-14 2018-03-14 Manica S P A Formulazione liquida di poltiglia bordolese ad alta efficacia
WO2019229495A1 (en) * 2018-05-29 2019-12-05 Copperprotek Spa. Microstructured multicomposite copper microparticle with antibacterial and/or biocidal activity that comprises 5 different types of copper compounds
IT201800006815A1 (it) * 2018-06-29 2019-12-29 An organic-inorganic hybrid material comprising a metal and lignin, processes for preparing the same and uses thereof / materiale ibrido organico-inorganico comprendente metallo e lignina, processi per la sua preparazione e suoi usi
WO2020021314A1 (en) * 2018-07-26 2020-01-30 Isagro S.P.A. Concentrated suspensions of copper salicylate and preparation process thereof
CN113303337A (zh) * 2021-06-02 2021-08-27 吴江市威士达铜业科技有限公司 硫酸铜钙的生产方法
WO2024152132A1 (es) * 2023-01-16 2024-07-25 Copperprotek Spa Lote maestro para producir un material antibacteriano para estar en contacto con la piel

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US3404951A (en) * 1966-09-09 1968-10-08 Takeda Chemical Industries Ltd Basic copper sulfate
US3725535A (en) 1970-10-22 1973-04-03 Cities Service Co Manufacture of basic cupric compounds
US4049801A (en) * 1973-01-12 1977-09-20 Philagro Phosphite compounds as fungicidal agents
FR2739256B1 (fr) * 1995-10-03 1997-10-24 Elf Atochem Agri Sa Bouillie bordelaise, son procede de fabrication et compositions fongicides cupriques la contenant
JPH10243807A (ja) * 1997-03-07 1998-09-14 Ykk Corp スライドファスナーの補強テープ
CN1330238C (zh) * 1997-04-25 2007-08-08 石原产业株式会社 防治有害生物的组合物和用该组合物防治有害生物的方法
FR2792501B1 (fr) * 1999-04-26 2004-02-06 Elf Atochem Agri Sa Traitement phytosanitaire des plantes par un chelate de cuivre soluble libere graduellement in situ a partir d'une source de cuivre non chelate et d'un chelate et compositions utilisables a cet effet

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Also Published As

Publication number Publication date
BRPI0409445A (pt) 2006-04-18
CN100556814C (zh) 2009-11-04
RU2362740C2 (ru) 2009-07-27
UA80480C2 (en) 2007-09-25
US8911794B2 (en) 2014-12-16
NZ543412A (en) 2009-06-26
US20070003635A1 (en) 2007-01-04
MXPA05011119A (es) 2006-03-17
WO2004094315A3 (fr) 2005-02-17
ZA200508935B (en) 2007-03-28
FR2853894B1 (fr) 2007-02-23
WO2004094315A2 (fr) 2004-11-04
EP1615853A2 (fr) 2006-01-18
CN1809509A (zh) 2006-07-26
AU2004232514B2 (en) 2011-09-29
FR2853894A1 (fr) 2004-10-22
AU2004232514A1 (en) 2004-11-04
BRPI0409445B1 (pt) 2013-02-05
RU2005135456A (ru) 2006-03-10

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